WO2011118400A1 - Plaque en titane et cuivre à haute résistance et procédé de fabrication de cette dernière - Google Patents

Plaque en titane et cuivre à haute résistance et procédé de fabrication de cette dernière Download PDF

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Publication number
WO2011118400A1
WO2011118400A1 PCT/JP2011/055599 JP2011055599W WO2011118400A1 WO 2011118400 A1 WO2011118400 A1 WO 2011118400A1 JP 2011055599 W JP2011055599 W JP 2011055599W WO 2011118400 A1 WO2011118400 A1 WO 2011118400A1
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titanium copper
copper plate
mbr
aging
less
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PCT/JP2011/055599
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English (en)
Japanese (ja)
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隆紹 波多野
真之 長野
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Jx日鉱日石金属株式会社
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Priority to KR1020127024358A priority Critical patent/KR101415438B1/ko
Priority to CN201180015912.0A priority patent/CN102822362A/zh
Publication of WO2011118400A1 publication Critical patent/WO2011118400A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
    • C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
    • C22F1/08—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of copper or alloys based thereon
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C9/00—Alloys based on copper

Definitions

  • the present invention relates to a titanium copper plate and a method of manufacturing the same, and a titanium copper plate suitably used for conductive spring materials such as connectors, terminals, relays and switches, and a method of manufacturing the same.
  • Titanium copper specified in JIS alloy No. C1990 is manufactured by performing cold rolling after solution treatment and then aging treatment.
  • Patent Document 1 a technique for improving bending workability as well as having high tensile strength and high proof strength by further cold rolling after solution treatment, cold rolling, and aging treatment of titanium copper has been reported.
  • the high strength titanium copper plate of the present invention contains 2.5 to 4.0% by mass of Ti, the balance being Cu and unavoidable impurities, and having a tensile strength of 950 MPa or more, 0.2%
  • Ratio (MBR / t) is 1.0 or less.
  • the average crystal grain size is 3 to 15 ⁇ m
  • the aspect ratio of crystal grains is 1.1 to 2.0
  • the metallographic structure of the rolling surface Preferably, the area ratio of the second phase particles having a diameter of more than 1 ⁇ m is 0 to 0.2%.
  • (MBR / t) is 0.5 or less
  • the aspect ratio of the crystal grains is 1.2 to 1.6
  • the area ratio of the second phase particles having a diameter of more than 1 ⁇ m is preferably 0 to 0.16%.
  • board thickness is 0.15 mm or less.
  • the method for producing a high strength titanium copper plate according to the present invention is a method for producing the high strength titanium copper plate, which comprises an ingot containing 2.5 to 4.0% by mass of Ti and the balance being Cu and unavoidable impurities. Hot rolling, cold rolling, solution treatment, aging treatment, and post-aging cold rolling at a working degree of 8 to 25% are performed in this order.
  • the solution treatment is preferably performed at 920 to 1050 ° C. for 5 to 50 seconds, and the aging treatment is preferably performed at 380 to 480 ° C. for 3 to 20 hours.
  • the post-aging cold rolling it is preferable to carry out strain relief annealing at 200 to 700 ° C. for 0.5 to 15 hours, or 300 to 600 ° C. for 10 to 1000 seconds.
  • a high strength titanium copper plate excellent in strength and bending workability can be obtained.
  • contact pressure at electrical contacts is obtained by applying elastic deformation of bending to a copper alloy strip.
  • the stress generated inside the copper alloy by bending exceeds the yield strength of the copper alloy, plastic deformation (swelling) occurs in the copper alloy, and the contact pressure decreases.
  • the higher the load resistance of the material the higher the contact pressure or springiness obtained.
  • the higher the tensile strength of the material the lower the bending workability. Therefore, it is necessary to achieve higher proof stress (0.9 times or more of tensile strength) with the same tensile strength.
  • the spring strength of the material required for the connector is improved by the level of proof strength rather than tensile strength.
  • the present inventors diligently investigate the relationship between the size and shape of crystal grains of the titanium copper plate and the state of the second phase particles (Cu-Ti-based compound) and the strength and bending workability. did. As a result, it was found that high strength and bending workability can be obtained by sequentially performing aging and cold rolling after solution treatment to improve strength and reducing coarse second phase particles.
  • the high strength titanium copper plate of the present invention has a tensile strength of 950 MPa or more and a 0.2% proof stress of 0.9 times or more of the tensile strength according to the following composition and other specifications.
  • the ratio (MBR / t) of the minimum bending radius (MBR) to the occurrence of cracking to the plate thickness (t) is 1.0 or less It has a characteristic. This can improve, for example, the springability and the bending processability required for a small electronic component.
  • the tensile strength is 1000 MPa or more
  • (MBR / t) is 0.5 or less
  • more preferably (MBR / t) is 0.2 or less.
  • the Ti concentration is set to 2.5 to 4.0 mass%. Titanium copper improves strength and conductivity by dissolving Ti into a Cu matrix by solution treatment and dispersing fine precipitates in the alloy by aging treatment. When the Ti concentration is less than 2.5% by mass, precipitation of precipitates is insufficient, and a tensile strength of 950 MPa or more can not be obtained. On the other hand, when the Ti concentration exceeds 4.0% by mass, bending workability deteriorates and (MBR / t) exceeds 1.0. It is preferable to set the Ti concentration to 2.9 to 3.4% by mass because the characteristics of (MBR / t) of 1.0 or less can be stably obtained with a tensile strength of 950 MPa or more.
  • 0 to 0.5 mass in total of one or more selected from the group consisting of Ag, B, Co, Cr, Fe, Mg, Mn, Mo, Nb, Ni, P, Si, V and Zr The incorporation of% can further improve the tensile strength.
  • the total content of these elements may be zero, that is, it may not contain these elements.
  • the total content of these elements exceeds 0.5% by mass, bending workability may be deteriorated, and (MBR / t) may exceed 1.0. More preferably, one or two or more of the above elements are contained in a total amount of 0.05 to 0.4% by mass.
  • the thickness of the high-strength titanium copper plate of the present invention is preferably 0.15 mm or less.
  • the high strength titanium copper sheet of the present invention tends to improve the bendability as the thickness becomes thinner and the value of (MBR / t) tends to become smaller, and when the thickness becomes 0.15 mm or less, the (MBR / t) becomes 1.0. It is because it becomes easy to achieve the following.
  • a more preferable thickness is 0.05 to 0.12 mm.
  • the average crystal grain size is 3 to 15 ⁇ m, and the aspect ratio of crystal grains is 1
  • the area ratio of second phase particles having a diameter of more than 1 ⁇ m is preferably 0 to 0.2% when the metallographic structure of the rolled surface is observed.
  • a cross section parallel to the rolling direction R and the thickness direction T is represented by a symbol S.
  • the average grain size is determined as follows. First, in the structure photograph of the cross section S, three straight lines are arbitrarily drawn in the thickness direction T, the number of crystal grains cut by the straight lines is determined, and the length of the straight lines divided by the number of crystal grains is a. . Similarly, three straight lines are drawn arbitrarily in the rolling direction L, the number of crystal grains cut by the straight lines is determined, and the length of the straight line divided by the number of crystal grains is defined as b. And let the value of (a + b) / 2 be an average grain size. Further, the value of b / a is taken as the aspect ratio of the crystal grain.
  • the second phase particles refer to a portion having a color tone different from that of the matrix (that is, a composition different from that of the matrix) when observing a secondary electron image of the metal structure after electropolishing the rolled surface.
  • This portion is a portion remaining without being dissolved by electrolytic polishing, and represents a second phase particle of Cu-Ti system such as Cu 3 Ti or Cu 4 Ti, and the portion having a diameter of 1 ⁇ m or more is bendable. Degrade the The area ratio of the second phase particles having a diameter of 1 ⁇ m or more is subjected to image analysis of the secondary electron image, and the diameter of the smallest circle including the area is determined for each of the matrix and different color tone areas. Let diameter.
  • FIG. 2 is an example of an actual secondary electron image of the metal structure after electropolishing the rolled surface of the high strength titanium copper plate of the invention example 2.
  • the average grain size is less than 3 ⁇ m, the solution treatment is insufficient, so non-recrystallized grains may remain locally or coarse second phase grains may remain, so bending workability is possible.
  • (MBR / t) may exceed 1.0. When the average grain size exceeds 15 ⁇ m, grain boundaries contributing to the strength may be reduced, and the tensile strength may be less than 950 MPa. Since a tensile strength of 950 MPa or more and (MBR / t) ⁇ 0.5 can be stably obtained, it is more preferable to set the crystal grain size to 3 to 12 ⁇ m.
  • the aspect ratio of crystal grains represents the degree of processing of the material, and the higher the aspect ratio, the higher the degree of processing. Therefore, when the aspect ratio of crystal grains is less than 1.1, the tensile strength may be less than 950 MPa. On the other hand, if the aspect ratio of the crystal grain exceeds 2.0, the processing becomes excessive and bending workability deteriorates, and (MBR / t) may exceed 1.0. It is more preferable to set the aspect ratio of the crystal grain to 1.2 to 1.6 because a tensile strength of 950 MPa or more and (MBR / t) ⁇ 1.0 can be stably obtained.
  • the area ratio of second phase particles having a diameter of more than 1 ⁇ m exceeds 0.2%, coarse second phase particles are present in the structure, so that bending processability is deteriorated, and (MBR / t) It may exceed 1.0. Since (MBR / t) ⁇ 1.0 is stably obtained, it is more preferable that the area ratio of the second phase particles having a diameter of more than 1 ⁇ m be 0.16% or less.
  • the method for producing a high strength titanium copper sheet according to the present invention comprises hot rolling, cold rolling, solution treatment, an ingot containing 2.5 to 4.0 mass% of Ti and the balance being Cu and unavoidable impurities. Aging and cold rolling after aging at a working degree of 8 to 25% are performed in this order. In the present invention, cold rolling is not performed between the solution treatment and the aging treatment. When this cold rolling is performed, although the tensile strength is slightly increased, the bending workability is deteriorated.
  • the ingot can be produced by melting and casting the material having the above composition, for example, as an ingot having a thickness of 100 to 300 mm. In order to prevent oxidation damage of titanium, it is preferable to carry out melting and casting in vacuum or in an inert gas atmosphere. Next, the ingot may be heated, for example, at 850 to 1000 ° C. for about 3 to 24 hours to perform hot rolling to a thickness of 3 to 30 mm.
  • the solution treatment is preferably performed using a continuous annealing furnace.
  • the solution treatment is performed at 920 to 1050 ° C. for 5 to 50 seconds, the above-described average crystal grain size can be adjusted to 3 to 15 ⁇ m.
  • the solution treatment conditions are adjusted so that the average grain size immediately after solution treatment becomes 3 to 15 ⁇ m. Good.
  • the aspect ratio of crystal grains changes as compared with that immediately after solution treatment. If the solution treatment temperature is less than 920 ° C.
  • the solution treatment is insufficient and partially unrecrystallized grains remain, so the average grain size is adjusted to 3 ⁇ m or more It tends to be difficult to adjust the area ratio of second phase particles having a diameter of more than 1 .mu.m to 0.2% or less. As a result, the bending workability of the obtained high strength titanium copper plate may be deteriorated, and (MBR / t) may exceed 1.0.
  • the solution treatment temperature exceeds 1050 ° C. or the solution treatment time exceeds 50 seconds, the solution treatment becomes excessive and the crystals grow too much, and the average crystal grain size may be adjusted to 15 ⁇ m or less It tends to be difficult.
  • a plurality of preliminary solution treatment may be performed prior to the solution treatment.
  • the conditions for the preliminary solution treatment are not particularly limited. If multiple preliminary solution treatments are performed, cold rolling may be performed between each solution treatment.
  • the aging treatment is preferably performed using a batch annealing furnace.
  • the aging treatment is preferably performed at 380 to 480 ° C. for 3 to 20 hours.
  • the aging treatment temperature is less than 380 ° C. or the aging treatment is less than 3 hours, sufficient precipitation (fine particles of Cu 3 Ti or Cu 4 Ti contributing to strength improvement) is not generated due to insufficient aging, and a tension of 950 MPa or more Achieving strength tends to be difficult.
  • the aging treatment temperature exceeds 480 ° C. or the aging treatment exceeds 20 hours, the precipitate becomes coarse due to overaging, and the tensile strength becomes less than 950 MPa and (MBR / t) becomes 1.0. May exceed.
  • the working ratio of cold rolling after aging is 8 to 25%.
  • the working degree is less than 8%, the tensile strength is less than 950 MPa, and the 0.2% proof stress does not reach 0.9 times or more of the tensile strength.
  • the degree of processing exceeds 25%, bending workability is poor, and (MBR / t) exceeds 1.0. Since a tensile strength of 950 MPa or more and (MBR / t) ⁇ 1.0 can be stably obtained, and a 0.2% proof stress stably reaches 0.9 times or more of the tensile strength, the processing degree is 10 It is more preferable to set it to -20%.
  • strain relief annealing may be performed after cold rolling after aging.
  • the strain relief annealing can be performed using a batch annealing furnace or a continuous annealing furnace.
  • the material is held in a 200 to 700 ° C. heating furnace for 0.5 to 15 hours. If the temperature of the batch annealing furnace is less than 200 ° C. or the holding time is less than 0.5 hours, it is difficult to sufficiently improve the spring limit value.
  • the temperature of the batch annealing furnace exceeds 700 ° C. or the holding time exceeds 15 hours, the tensile strength decreases.
  • the material is held in a heating furnace at 300 to 600 ° C. for 10 to 1000 seconds. If the temperature of the continuous annealing furnace is less than 300 ° C. or the holding time is less than 10 seconds, it is difficult to sufficiently improve the spring limit value. When the temperature of the continuous annealing furnace exceeds 600 ° C. or the holding time exceeds 1000 seconds, the tensile strength decreases.
  • processes such as grinding, polishing, shot blasting and pickling for removing oxide scale on the surface can be appropriately performed between the above respective processes.
  • Electrolytic copper was melted in a vacuum melting furnace, and Ti and other elements (subcomponents of Tables 1 and 2) were added in the proportions shown in Tables 1 and 2. This molten metal was cast to obtain a rectangular ingot having a thickness of 150 mm, a width of 600 mm, and a length of 6000 mm. The ingot was heated at 950 ° C. for 3 hours, and hot rolled into a hot-rolled sheet with a thickness of 10 mm.
  • strain relief annealing was performed at 300 ° C. for 3 hours in a batch annealing furnace, or at 500 ° C. for 10 seconds in a continuous annealing furnace. The following characteristic evaluation was performed about the sample after cold rolling after aging (after strain relief annealing after strain relief annealing).
  • the spring limit value in the direction parallel to the rolling direction was measured by a moment test prescribed in JIS-H3130. (Average grain size and aspect ratio) After finishing the rolling direction and parallel to the cross section of the sample (S in FIG. 1) to a mirror surface by mechanical polishing, water (100mL) -FeCl 3 (5g) grain boundaries by etching using a-HCl (10 mL) solution of the current The tissue was photographed using an optical microscope. On the photograph of the structure, three straight lines are arbitrarily drawn in the thickness direction T, the number of crystal grains cut by the straight line is determined, and a value obtained by dividing the length of the straight line by the number of crystal grains is a.
  • the lightness of the observation field of view is binarized with the threshold value 60, and the diameter of the smallest circle including the area is determined for each of the matrix and different areas of color tone. It was the diameter of the two-phase particle. And the value which divided the total area of the 2nd phase particle of diameter 1 micrometer or more by the total area of the observation visual field was made into the area ratio.
  • the tensile strength is 950 MPa or more, the 0.2% proof stress is 0.9 times or more of the tensile strength, and (MBR / t) is 1 .0 or less, and both strength and bending workability were excellent.
  • the tensile strength is 1000 MPa or more, the 0.2% proof stress is 0.9 times or more of the tensile strength, and (MBR / t) is 0.5 or less It was excellent in both strength and bending workability.
  • Comparative Example 1 In the case of Comparative Example 1 in which the Ti concentration is less than 2.5%, the tensile strength is less than 950 MPa. On the other hand, in the case of Comparative Example 2 in which the Ti concentration exceeded 4.0%, bending workability decreased and (MBR / t) exceeded 1.0. In the case of Comparative Example 3 in which the plate thickness is more than 0.15 mm, bending workability is reduced, and (MBR / t) exceeds 1.0.
  • Comparative Example 4 In the case of Comparative Example 4 in which the working ratio of cold rolling after aging is less than 8%, the aspect ratio of the crystal grains is less than 1.1, the tensile strength is reduced to less than 950 MPa, and the 0.2% proof stress is tensile strength Less than 0.9 times the
  • Comparative Example 5 in which the working ratio of cold rolling after aging exceeded 25%, the aspect ratio exceeded 2.0, the bending workability decreased, and (MBR / t) exceeded 1.0. .
  • Comparative Example 11 In the case of Comparative Example 11 in which cold rolling before aging was performed between solution treatment and aging treatment in addition to cold rolling after aging, bending formability was reduced, and (MBR / t) was It exceeded 1.0. Comparative Example 11 was manufactured under the same conditions as Inventive Example 2 except that cold rolling before aging was performed, and although the tensile strength was slightly increased (20 MPa), the bending workability decreased. It can be seen that
  • Comparative Example 12 in which cold rolling before aging was performed between solution treatment and aging treatment in addition to cold rolling after aging, bending formability is reduced (MBR / t) exceeded 1.0.
  • Comparative Example 12 was manufactured under the same conditions as Inventive Example 11 except that cold rolling before aging was performed, and although the tensile strength was slightly increased (11 MPa), the bending workability decreased. It can be seen that Moreover, the total processing degree ( ⁇ (plate thickness at the time of solution treatment)-(final plate thickness)) / (plate thickness at the time of solution treatment ⁇ 100) of Comparative Example 12 is 20%, and the total processing rate is It can be seen that the bending workability is deteriorated even in comparison with the same invention example 12.

Abstract

La présente invention se rapporte à une plaque en titane et cuivre qui présente une excellente résistance, une excellente conductivité et une excellente aptitude à la flexion, et à un procédé de fabrication de cette dernière. La plaque en titane et cuivre à haute résistance comprend une quantité de titane (Ti) comprise entre 2,5 et 4,0 % en masse, le restant étant du cuivre (Cu) et des impuretés inévitables. La résistance à la traction est d'au moins 950 MPa, la limite élastique conventionnelle de 0,2 % fait 0,9 fois la résistance à la traction et le rapport (MBR/t) entre l'épaisseur (t) de la plaque et le rayon de flexion minimal (MBR) auquel il ne se produit pas de cassure, est inférieur ou égal à 1,0 lorsqu'un essai de flexion (W) est effectué de telle manière que l'axe de flexion soit parallèle à la direction de laminage.
PCT/JP2011/055599 2010-03-25 2011-03-10 Plaque en titane et cuivre à haute résistance et procédé de fabrication de cette dernière WO2011118400A1 (fr)

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KR1020127024358A KR101415438B1 (ko) 2010-03-25 2011-03-10 고강도 티탄 구리판 및 그 제조 방법
CN201180015912.0A CN102822362A (zh) 2010-03-25 2011-03-10 高强度钛铜板及其制造方法

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JP2010069470A JP4761586B1 (ja) 2010-03-25 2010-03-25 高強度チタン銅板及びその製造方法
JP2010-069470 2010-03-25

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KR (1) KR101415438B1 (fr)
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WO2021258747A1 (fr) * 2020-06-24 2021-12-30 宁波博威合金板带有限公司 Bande d'alliage bronze-titane contenant nb et al et son procédé de préparation

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JP5542898B2 (ja) * 2012-10-24 2014-07-09 Ｊｘ日鉱日石金属株式会社 カメラモジュール及びチタン銅箔
JP6192916B2 (ja) * 2012-10-25 2017-09-06 Ｊｘ金属株式会社 高強度チタン銅
JP5885642B2 (ja) * 2012-11-15 2016-03-15 Ｊｘ金属株式会社 カメラモジュール及びチタン銅箔
US20150115442A1 (en) * 2013-10-31 2015-04-30 Infineon Technologies Ag Redistribution layer and method of forming a redistribution layer
JP5718443B1 (ja) 2013-12-27 2015-05-13 Jx日鉱日石金属株式会社 電子部品用チタン銅
CN104372234B (zh) * 2014-10-29 2017-01-11 嵊州市博纳五金机械厂 高耐磨型钛铜镍硅合金复合材料及其制备方法
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CN107267799B (zh) * 2017-06-22 2019-03-08 安徽晋源铜业有限公司 一种铬锆铜合金材料及其制备方法
CN108588477B (zh) * 2018-05-15 2020-06-26 西安理工大学 一种高强度导电弹性Cu-Ti-Ni-Y合金及其制备方法
CN108559859B (zh) * 2018-05-15 2020-06-26 西安理工大学 一种高强度导电Cu-Ti-Ni-Si合金及其制备方法
CN108642318B (zh) * 2018-05-15 2020-09-25 西安理工大学 一种导电弹性Cu-Ti-Ni-Ag合金及其制备方法
CN108950292B (zh) * 2018-07-24 2020-07-24 西安理工大学 一种导电弹性Cu-Ti-Ni-Al合金及其制备方法
CN111101016B (zh) * 2020-02-26 2021-01-19 宁波博威合金材料股份有限公司 一种时效强化型钛铜合金及其制备方法
CN113278844B (zh) * 2021-05-18 2022-05-27 国工恒昌新材料沧州有限公司 一种高强度高弹性铜钛合金及其制造方法

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WO2021258747A1 (fr) * 2020-06-24 2021-12-30 宁波博威合金板带有限公司 Bande d'alliage bronze-titane contenant nb et al et son procédé de préparation

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CN102822362A (zh) 2012-12-12
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TW201137134A (en) 2011-11-01
KR101415438B1 (ko) 2014-07-04
TWI421354B (zh) 2014-01-01

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